|Publication number||US4766174 A|
|Application number||US 06/815,599|
|Publication date||Aug 23, 1988|
|Filing date||Jan 2, 1986|
|Priority date||Jan 2, 1986|
|Also published as||CA1261986A, CA1261986A1, CN1009102B, CN87100006A, DE3687644D1, DE3687644T2, EP0228916A2, EP0228916A3, EP0228916B1|
|Publication number||06815599, 815599, US 4766174 A, US 4766174A, US-A-4766174, US4766174 A, US4766174A|
|Inventors||Robert J. Statz|
|Original Assignee||E. I. Du Pont De Nemours And Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (12), Referenced by (29), Classifications (27), Legal Events (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
This invention relates to aluminum ionomers and more particularly it relates to melt processible aluminum ionomer blends.
2. Description of the Prior Art
Aluminum ionomer blends are useful where sodium or zinc ionomers cannot be used because of their temperature limitations. Sodium and zinc ionomers of ethylenically unsaturated carboxylic acid copolymers have no resistance to compression set at 70° C. and at 70°-100° C. they loose all of their physical strength. Unlike these ionomers, aluminum ionomers maintain useful physical properties above 100° C. However, neat aluminum ionomers are not melt processible using standard thermoplastic processing techniques, such as injection molding or extrusion.
Japanese Patent Publication No. 56-55442 discloses a resin composition having improved properties comprising an ionically crosslinked copolymer of ethylene and alpha,beta-ethylenically unsaturated carboxylic acid, partially or completely ionically crosslinked by metal ion optionally an alpha,beta-unsaturated ester, and a polyamide resin having a melting point of not more than 160° C. Ten mole percent or more of the alpha,beta-unsaturated carboxylic acid component is disclosed to be substituted by Na+, Mg2+, Zn2+, Al3+, and the like. It is disclosed that the resin composition "can be prepared by a known blending method; the composition is processed into a powder, chips, pellets, or the like form followed by feeding to an extruder, injection molder, compression molding machine or the like to form films, sheets, tubes, molded articles, or the like." It is further taught that "It is permissible to directly feed to the above molding equipment the ionically crosslinked copolymer together with the polyamide resin in the form of a powder, chips, pellets, or the like." The examples disclose ionomers neutralized with magnesium, zinc and sodium ions.
U.S. Pat. No. 4,187,358 discloses a resin composition of (1) an aromatic copolyester derived from (a) a mixture of terephthalic and isophthalic acid and (b) a bisphenol, (2) a polyamide, and (3) an ionomer.
The ionomer is disclosed to be a base copolymer and the product obtained by reacting the base copolymer with a metal compound capable of ionizing the copolymer. The base copolymer is an alpha-olefin/alpha, beta-unsaturated carboxylic acid copolymer e.g., ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/itaconic acid copolymer, ethylene/maleic acid copolymer, ethylene/methacrylic acid/vinyl acetate copolymer, ethylene/acrylic acid/vinyl alcohol copolymer, etc. As the metallic ion suitable for neutralizing the carboxylic acid group of the base copolymer metal ions of the groups IA, IB, IIA, IIB, and IIIA of the periodic Table are disclosed to be preferable, the metallic ions having an aromatic valence of 1 to 3 (e.g. Na+, K+, Li+, Cu2+, Be2+, Zn2+ and Al3+). The ionomer can be produced by reacting the base copolymer with a formate, acetate, hydroxide, methoxide, carbonate, etc. of the above metals. It is also disclosed that acidic olefinic copolymers that are not reacted with metallic ion can also be used. These are obtained by mixing the acidic olefinic copolymer with polyamide and the specified aromatic copolyester without adding metallic ion. It is further disclosed that it is also possible to form a resin composition by adding the metallic ion while melt extruding an acidic olefinic copolymer, a polyamide and/or specified aromatic copolyester, thus neutralizing the acidic olefinic copolymer.
The ionomer is disclosed to be a very soft substance with a heat distortion temperature measured by ASTM-D648 (18.6 kg/cm2) of below room temperature.
The examples only disclose ionomers neutralized with zinc and sodium ions.
It is disclosed that the resin composition can be prepared by mixing the three ingredients by any of the known methods e.g. kneading through a kneader or rollers or melt extruding through an extruder or finely pulverizing and mixing in a super mixer and then pressforming or rotational molding. It is further disclosed that the sequence in which the materials are mixed is optional i.e. three ingredients may be mixed at the same time or two of them mixed first and the third ingredient added later. In some cases, in order to obtain improved properties, it is preferable to melt mix the specified aromatic copolyester and polyamide first and mixing the resulting composition with an ionomer in the molten state or melt mixing the ionomer and the polyamide to form a composition and then mixing the resulting composition with the specified aromatic copolyester in the molten state.
According to the present invention there is provided a process for preparing a melt processible blend of aluminum ionomer and thermoplastic resin or elastomer by
(A) mixing at from about 150° to about 300° C.
(a) from about 50 to about 95% by weight of direct or graft copolymer of ethylene, alpha,beta-ethylenically unsaturated carboxylic acid having from 3 to 8 carbon atoms, and softening comonomer selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl group contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms, and wherein the ethylene content of the polymer is from about 30 to about 98 weight percent, the carboxylic acid content is from about 1 to about 25 weight percent and the softening comonomer content is from 0 to about 60 weight percent, and
(b) from about 5 to about 50% by weight of at least one thermoplastic resin or thermoplastic elastomer selected from the group consisting of polyamide (e.g. nylon 66, nylon 6, nylon 610, nylon 612, nylon 666), polyester (e.g. polyethylene terephthalate, poly tetramethylene glycol terephthalate) polyester ether, block copolymer of aromatic substituted ethylenically unsaturated monomer with diolefin and hydrogenated derivative of said copolymer (e.g. styrene/butadiene block copolymer), polyurethane, and polyolefin resin, and
(B) subsequent to or simultaneously with said mixing neutralizing from about 1 to about 100% of the carboxylic acid groups with an aluminum ion source provided, however that when the thermoplastic resin or thermoplastic elastomer is polyamide, polyester, polyester ether or polyurethane the aluminum ion source is selected from the group consisting of (1) chelated aluminum compound and (2) mixture of aluminum alkoxide with aluminum acetylacetonate or with acetylacetone.
It was discovered that by blending ethylene/unsaturated carboxylic acid copolymers with selected high melting thermoplastic resins or elastomers and simultaneously or subsequently converting these blends to aluminum ionomers it is possible to obtain blends of Al ionomers with thermoplastic resins and/or thermoplastic elastomers which have resistance to compression set and excellent tensile properties and sag resistance at elevated temperatures. In addition, these aluminum ionomer blends retain the excellent oil and abrasion resistance and the excellent resilience of standard ionomers.
The blends prepared according to the present invention can be used as thermoplastic resins and thermoplastic elastomers in such applications as automotive body side moldings, ski boots, tubing and hydraulic hose jackets.
The blend of the present invention contains an aluminum ionomer and a thermoplastic resin or thermoplastic elastomer.
The aluminum ionomer is derived from direct or graft copolymer of ethylene, alpha,beta-ethylenically unsaturated carboxylic acid and optionally softening comonomer.
The unsaturated carboxylic acid has from 3 to 8 carbon atoms. Such acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and half esters of maleic, fumaric and itaconic acids. Preferably the acid is acrylic or methacrylic acid, and most preferably the acid is methacrylic acid.
The softening comonomer is selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl group contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms. Accordingly suitable softening comonomers are for example vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, butyl vinyl ether, and methyl vinyl ether. Preferably the softening comonomer is alkyl acrylate, alkyl methacrylate or alkyl vinyl ether, and most preferably the softening comonomer is butyl acrylate.
The ethylene/acid copolymer contains from about 30 to about 95% by weight of ethylene, from about 1 to about 25% by weight of unsaturated carboxylic acid, and from 0 to about 60% by weight of softening comonomer. Preferably the copolymer contains from about 50 to 95% by weight of ethylene, from about 5 to about 20% by weight of unsaturated carboxylic acid and from 0 to about 40% by weight of softening comonomer. Most preferably the copolymer contains from about 60 to about 95% by weight of ethylene, from about 5 to about 15% by weight of unsaturated carboxylic acid and from 0 to about 30% by weight of softening comonomer.
These ethylene/acid copolymers are blended with a thermoplastic resin or thermoplastic elastomer. The thermoplastics should be nonreactive with the aluminum ion source (i.e. the thermoplastics should have little or no acid functionality) and they should have at least a slight degree of compatibility with the ethylene acid copolymer to avoid grossly incompatible blends that are laminar.
Accordingly, the thermoplastic resin or elastomer can be polyamide (e.g. nylon 66, nylon 6, nylon 610, nylon 612, nylon 666), polyester (e.g. polyethylene terephthalate, poly tetramethylene glycol terephthalate), polyester ether (containing a crystalline phase consisting of the polyester of alkane diols having 4 to 8 carbon atoms with aromatic diacids and a soft rubbery polyether phase), block copolymer of aromatic substituted ethylenically unsaturated monomer with diolefin (e.g. styrene/butadiene and hydrogenated derivative of said copolymer), polyurethane, and polyolefin resin (e.g. polyethylene or polypropylene). Preferably the thermoplastic resin or elastomer is nylon, polyolefin or A-B-A type block copolymer of aromatic substituted ethylenically unsaturated monomer (A) with diolefin (B) and hydrogenated derivatives of said copolymers. Most preferably, the thermoplastic resin or elastomer is nylon 6, high density polyethylene or hydrogenated A-B-A block copolymer of styrene (A) with a mixture of butadiene and isoprene (B).
The amount of ethylene/acid copolymer in the blend is from about 50 to about 95% by weight, preferably from about 55 to about 90% by weight, and most preferably from about 60 to about 80% by weight. The thermoplastic resin or elastomer is present in an amount of from about 5 to about 50% by weight, preferably from about 10 to about 45% by weight, and most preferably from about 20 to about 40% by weight.
After the ethylene/acid copolymer and the thermoplastic resin or elastomer has been mixed, the blend is neutralized with an aluminum ion source, such as aluminum carboxylate, aluminum alkoxide, chelated aluminum compounds, and aluminum hydroxide, preferably aluminum acetate, aluminum isopropoxide and aluminum acetylacetonate.
Care should be taken when the thermoplastic resin or elastomer is hydrolyzable, such as polyamides, polyesters, polyester ethers or polyurethanes. When the blend of the present invention is made with such polymers it is essential that the aluminum ion source does not generate water or acid during the course of the neutralization, in order to avoid degradation of the thermoplastic resin or elastomer. Suitable aluminum ion source for such sensitive polymers are chelated aluminum compounds and mixtures of aluminum alkoxides with chelated aluminum compounds or with functional amounts of chelating agents. Preferred aluminum ion source for the sensitive polymers is aluminum acetylacetonate and aluminum dialkoxide acetoacetic ester chelate (e.g. aluminum diisopropoxide acetoacetic ester chelate) and mixtures of aluminum isopropoxide with aluminum acetylacetonate or with dialkoxide acetoacetic ester chelate or with acetylacetone or with acetoacetic ester. The most preferred aluminum ion source for the sensitive polymers is aluminum acetylacetonate and for the nonhydrolyzable polymers, such as aromatic/diolefin block copolymers and polyolefin resins it is alumina trihydrate activated with glacial acetic acid.
The extent of neutralization is from about 1 to about 100%, preferably from about 5 to about 90% and most preferably from about 10 to 85%.
The blends of ethylene/acid copolymer and thermoplastic resin or elastomer can be prepared by mixing at a temperature of from about 150° to about 300° C., preferably from about 180° C. to about 295° C. and most preferably from about 200° C. to about 290° C. the ethylene acid copolymer with the thermoplastic material and subsequently neutralizing the material with an aluminum ion source. Alternatively the mixing and neutralization can be carried out simultaneously. Production of the neat aluminum ionomer followed by mixing with the thermoplastic component is precluded by the intractability of the aluminum ionomer.
The following examples serve to illustrate the present invention. All parts, percentages and proportions are by weight unless otherwise indicated.
An ethylene, n-butylacrylate, methacrylic acid polymer containing 30% butyl acrylate, 5% methacrylic acid and 65% ethylene (77 grams) was placed on a roll mill with ethylene/methacrylic acid copolymer containing 1.7% methacrylic acid (14 grams) and linear ethylene/octene-1 copolymer of 0.45 g/10 min MI and 0.95 g/cm3 density (about 1% by weight octene content) (7.6 grams). This material was fluxed together at 190° C. and enough aluminum acetylacetonate (Alacac) was added in order to neutralize 28% of the acid (1.4 grams). The material was milled for about 5-10 minutes and removed from the mill and molded into plaques using a compression molding device.
The composition and physical properties of these compression molded samples are summarized in Table I.
TABLE I______________________________________ Example 1______________________________________Composition, g 65 E/30nBA/5MAA (77) 98.3 E/1.7 MAA (14) ethylene copolymer.sup.(9) (7.6) Alacac (1.4) 28% neutr.Hardness Shore A.sup.(1) 65Compression Set.sup.(2)Method B 22 hrs. @ 70° C. 4885° C. 73Tensile Strength @ 23° C..sup.(3)Breakpsi 790MPa 5.45% elongation 350Tensile Strength 100% strainpsi.sup.(3) 500MPa 3.45Tensile Set at 100% strain, % 8Tensile Strength @ 70° C.psi.sup.(5) 329MPa 2.29Flex Modulus.sup.(4) psi MPa70° C. 500 3.4450° C. 730 5.0323° C. 1840 12.69-20° C. 3640 25.09-30° C. 5020 34.61Ross Flex @ -29° C., cycles.sup.(5) 5000Bashore resilience, % rebound.sup.(6) 39Oil Swell 100° C. ASTM No. 3.sup.(7) 236% Swell 70 hrs. 236Clash-Berg ° C..sup.(8) -32______________________________________ Footnotes .sup.(1) ASTM D2240 .sup.(2) ASTM D395 .sup.(3) ASTM D412 .sup.(4) ASTM D790 .sup.(5) ASTM D1052 .sup.(6) ASTM D2632 .sup.(7) ASTM D471 .sup.(8) ASTM D1043 .sup.(9) linear ethylene/octene1 copolymer having 0.45 MI and 0.95 densit containing about 1% by weight of octene1
Twenty four hundred grams of an ethylene/n-butyl acrylate/methacrylic acid copolymer (60E/28 nBA/12 MAA) and 1028 g of unextracted polycaprolactam (nylon 6) 178 g of aluminum acetylacetonate, and 255 g of N-ethyl-p-toluene sulfonamide was extrusion compounded on a Werner & Pfleiderer twin-screw extruder using the conditions indicated in Table A:
TABLE A__________________________________________________________________________Compounding Conditions Temperature °C.ExampleRPM Amps Volts Rear Rear-Center Center Front-Center Front Die Melt Vacuum__________________________________________________________________________2 150 11 135 109 210 236 253 257 191 277 26.5 in.Hg (89.5 kPa)__________________________________________________________________________
Plaques were produced by injection molding using a 3 oz. (85.1 g) machine under conditions indicated in Table II. The physical properties of the plaques are summarized in Table III.
TABLE II__________________________________________________________________________INJECTION MOLDING CONDITIONS Screw BackTemperature °C. Boost/Inject/ Press. Ram Speed Press.ExampleRear Center Front Nozzle Mold Hold Sec psi (MPa) Speed rpm psi (MPa)__________________________________________________________________________2 110 187 242 248 90 2/20/25 1200-1600 fast 60 50 (8.3-11.0) (0.34)__________________________________________________________________________
TABLE III______________________________________ Example 2______________________________________Shore Hardness 95ACompression set, % 55@ 70° C. 22 hrs.Tensile Strength at break,psi 2800MPa 19.31% elongation 180Tensile Strength at breakat 100° C.,psi 1400MPa 9.65% elongation 70NBS abrasion 590IndexOil Swell, %100° C. 70 hrs.ASTM No. 3 47ASTM No. 1 8.7Flex Modulus,psi 12,200MPa 84.1Clash-Berg °C. -10______________________________________
The blends and plaques of the present Examples were prepared in the same manner as described in Example 2. Comparative Example 1 shows the results of the blend of a zinc ionomer and a nylon molding resin. The compositions and physical properties are summarized in Table IV.
At similar degrees of neutralization and nylon levels zinc ionomer blends give much poorer tensiles at elevated temperatures and poorer resistance to compression set.
TABLE IV__________________________________________________________________________Example 3 4 5 6__________________________________________________________________________Ethylene Copolymer 80E/10iBA/10MAA 66E/27nBA/7MAA 66E/27nBA/7MAA 66E/27nBA/7MAA 35 MI 22 MI 22 MIEthylene Copolymer 65 65 65 65Phase, %% Neutralization, 40 (Al) 20 (Al) 40 (Al) 60 (Al)(ion)High Melting Unextracted polycaprolactam (nylon 6), I.V. 65Thermoplastic ResinPhase, 35 35 35 35Amount %Hardness, Shore A 90 80 80 85Tens. Str. @ 23° C.MPa 15.5 7.93 11.4 14.7psi 2250 1150 1650 2125% Elongation 120 240 260 130Tens. Str. @ 100° C.MPa 2.2 0.69 1.9 4.2psi 320 100 280 610% Elongation 50 110 35 50Compression Set % 80 69 64 6670° C., Method B,22 hrs__________________________________________________________________________Example 7 8 9 C-1__________________________________________________________________________Ethylene Copolymer 66E/27nBA/7MAA 66E/27nBA/7MAA 80E/10iBA/10MAA 66E/27nBA/7MAAEthylene Copolymer 80 80 80 65Phase, %% Neutralization, 20 (Al) 40 (Al) 60 (Al) 60 (Zn)(ion)High Melting Unextracted polycaprolactam (nylon 6), I.V. 65Thermoplastic ResinPhase, 20 20 20 35Amount %Hardness, Shore A 75 85 80 88Ten. Str. @ 23° C.MPa 5.17 9.83 16.4 11.2psi 750 1425 2375 1625% Elongation 300 60 130 15Ten. Str. @ 100° C.MPa 0.55 1.9 5.5 1.4psi 80 280 800 200% Elongation 105 20 60 10Compression Set %70° C., Method B, 70 75 63 7722 hrs__________________________________________________________________________
The blends and plaques of the present Examples were prepared in the same manner as described in Example 1. The compositions and physical properties are summarized in Table V. The results demonstrate that aluminum ionomer blends can be produced using polypropylene, polyester ether and thermoplastic polyurethanes as the high melting thermoplastic phase.
TABLE V__________________________________________________________________________Example 10 11 12__________________________________________________________________________Ethylene Copolymer 66E/27nBA/7MAA 66E/27nBA/7MAA 66E/27nBA/7MAA 22 MI 22 MI 22 MIEthylene Copolymer 70 70 70Phase, %% Neutralization with 65 65 68Aluminum ionsHigh Melting Thermo- polypropylene.sup.(1) polyester ether.sup.(2) thermoplasticplastic Phase (%) (30) (30) polyurethane.sup.(3) (30)Hardness, Shore D 40 32 35Tensile Str. @ 23° C.MPa 13.8 10.3 8.62psi 2000 1500 1250% elongation 415 180 90Tensile Str. @ 100° C.MPa 3.4 2.2 2.2psi 500 320 320% elongation 200 15 30Compression Set % 70 57 66@ 70° C. 20 hrs.__________________________________________________________________________ Footnotes .sup.(1) homopolymer of propylene, density 0.902 g/cm3, M.I. 0.4 g/1 min at 220° C. .sup.(2) polyester ether containing a crystalline phase consisting of the polyester of 1,4butanediol with terephthalic acid and a soft rubbery polytetramethylene ether glycol phase .sup.(3) polyurethane containing a crystalline phase consisting of the addition product of 4,4'-diphenyl methane diisocyanate with 1,4butanediol and a soft rubbery phase consisting of the polyester of 1,4butanediol wit adipic acid
The blends and plaques of the present Examples were prepared in the same manner as described in Example 2. The compositions and physical properties are summarized in Table VI. The data indicate that at low degrees of neutralization tensile properties and elongation are superior. At lower nylon levels high temperature properties are inferior.
TABLE VI__________________________________________________________________________Example 13 14 15__________________________________________________________________________Ethylene 65E/25nBA/10MAA 65E/25nBA/10MAA 65E/25nBA/10MAACopolymer 65 65 65amount, %Nylon 6, % 28 28 28N--ethyl-p-toluene 7 7 7sulfonamide, %% Neutralization with 23 46 66Aluminum ionsTen. Str. Break@23° C.MPa 15.9 13.8 12.4psi 2300 2000 1800% elong. 260 100 50Ten. Str. Break@100° C.MPa 4.5 3.6 3.8psi 660 520 550% elong. 90 45 20Clash -8 -9 -10Berg, °C.Sag test 0 0 0@ 121° C.cm deflection__________________________________________________________________________Example 16 17 18__________________________________________________________________________Ethylene 66E/27nBA/7MAA 66E/27nBA/7MAA 66E/27nBA/7MAACopolymer 65 68.7 70.3amount, %Nylon 6, % 28 24 22N--ethyl-p-toluene 7 7.3 7.7sulfonamide, %% Neutralization with 49 49 49Aluminum ionsTen. Str. Break@ 23° C.MPa 8.61 7.58 6.89psi 1250 1100 1000% elong. 30 20 20Ten. Str. Break@ 100° C.MPa 3.3 4.1 2.1psi 480 600 300% elong. 20 20 20Clash - - -Berg, °C.Sag test 0 0 0.5@ 121° C.cm deflection__________________________________________________________________________
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|U.S. Classification||525/64, 525/195, 525/66, 525/78, 525/173, 525/71, 525/919, 525/131, 525/183, 525/93, 525/176, 525/196|
|International Classification||C08L23/26, C08L7/00, C08L77/00, C08L33/02, C08L51/00, C08L51/02, C08F8/44, C08L33/00, C08L21/00, C08L23/00, C08L101/00, C08L67/00|
|Cooperative Classification||Y10S525/919, C08F8/44|
|Feb 24, 1986||AS||Assignment|
Owner name: E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, D
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:STATZ, ROBERT J.;REEL/FRAME:004512/0706
Effective date: 19851230
|Jan 29, 1992||FPAY||Fee payment|
Year of fee payment: 4
|Jan 24, 1996||FPAY||Fee payment|
Year of fee payment: 8
|Mar 14, 2000||REMI||Maintenance fee reminder mailed|
|Aug 20, 2000||LAPS||Lapse for failure to pay maintenance fees|
|Oct 24, 2000||FP||Expired due to failure to pay maintenance fee|
Effective date: 20000823